CN107629448A - A kind of preparation method with sandbag structure block polyetheramides expanded particle - Google Patents

A kind of preparation method with sandbag structure block polyetheramides expanded particle Download PDF

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Publication number
CN107629448A
CN107629448A CN201711053875.8A CN201711053875A CN107629448A CN 107629448 A CN107629448 A CN 107629448A CN 201711053875 A CN201711053875 A CN 201711053875A CN 107629448 A CN107629448 A CN 107629448A
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China
Prior art keywords
particle
block polyetheramides
blending
preparation
sandbag structure
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CN201711053875.8A
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Chinese (zh)
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CN107629448B (en
Inventor
顾飚
董卫龙
夏洋
巢熊飞
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Changzhou Shunxiang New Material Technology Co Ltd
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Changzhou Shunxiang New Material Technology Co Ltd
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Priority to CN201711053875.8A priority Critical patent/CN107629448B/en
Priority to JP2019527498A priority patent/JP6852921B2/en
Priority to PCT/CN2017/115520 priority patent/WO2019085158A1/en
Priority to US16/469,974 priority patent/US11124619B2/en
Priority to EP17917218.4A priority patent/EP3517574A4/en
Priority to KR1020197023864A priority patent/KR102263684B1/en
Publication of CN107629448A publication Critical patent/CN107629448A/en
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    • C08J9/16—Making expandable particles
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    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
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    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
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    • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
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    • C08J2201/00—Foams characterised by the foaming process
    • C08J2201/02—Foams characterised by the foaming process characterised by mechanical pre- or post-treatments
    • C08J2201/022—Foams characterised by the foaming process characterised by mechanical pre- or post-treatments premixing or pre-blending a part of the components of a foamable composition, e.g. premixing the polyol with the blowing agent, surfactant and catalyst and only adding the isocyanate at the time of foaming
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Abstract

The present invention relates to a kind of preparation method with sandbag structure block polyetheramides expanded particle, comprise the following steps：S1, by modifying agent, filler, coupling agent premix, then by after premix raw materials melt be blended, the blending particle I with core shell structure is prepared after granulation underwater or tank pelletizing；S2, particle I and block polyetheramides raw material premix will be blended, then the raw materials melt after premix will be blended, and the block polyetheramides with sandbag structure be made after granulation underwater or tank blank particle II is blended；S3, particle II will quantitatively be blended put into autoclave, quantitative environment-friendly physical blowing agent is passed through again, the pressure in kettle is emptied after foaming agent and G2 blending particles reach homogeneous system, then by relief valve, takes out the block polyetheramides blending particle III containing foaming agent；S4, blending particle III moved into and risen in the thermostatic equipment of the particle softening temperature, the block polyetheramides expanded particle with sandbag structure is obtained after insulation.

Description

A kind of preparation method with sandbag structure block polyetheramides expanded particle
Technical field
The present invention relates to foam material field, and in particular to a kind of with sandbag structure block polyetheramides expanded particle Preparation method.
Background technology
Block polyetheramides foamed material is typically prepared by organic chemistry foaming in the prior art, the preparation technology has Two shortcomings：Although the first, can partly improve the physical property of product using crosslinking agent, crosslinking agent can cause the production prepared Product can not be recycled again, waste of resource；2nd, being mixed into for organic chemistry foaming is to utilize kneader and block polyether acyl Amine is blended, and the mixing of one side solid and solid can not possibly reach homogeneous system so that each local uniform in foaming It cannot be guaranteed, still further aspect, the presence of the organic foaming agent retained after foaming has a great impact to the performance of product.
In view of it is above-mentioned the defects of, the design people, be actively subject to research and innovation, a kind of new there is sandbag knot to found The preparation method of structure block polyetheramides expanded particle, make it with more the value in industry.
The content of the invention
In order to solve the above technical problems, sent out it is an object of the invention to provide a kind of by modifying agent with environment-friendly physics Infusion, the method for preparing high performance sandbag structure block polyetheramides expanded particle.
Technical scheme is as follows：
A kind of preparation method with sandbag structure block polyetheramides expanded particle, it is characterised in that including following step Suddenly：
S1, by modifying agent, filler, coupling agent premix, then by after premix raw materials melt be blended, through granulation underwater or tank The blending particle I with core shell structure is prepared after pelletizing；
S2, the blending particle I that step S1 is prepared and block polyetheramides raw material premix, then by the raw material after premix Melt blending, the block polyetheramides blending particle II with sandbag structure is made after granulation underwater or tank blank；
S3, particle II will quantitatively be blended put into autoclave, autoclave is adjusted to certain temperature and keeps constant temperature, then is passed through Quantitative environment-friendly physical blowing agent, through certain time of penetration until foaming agent and G2 blending particles reach homogeneous system Afterwards, then by relief valve by the pressure in kettle empty, take out the block polyetheramides blending particle III containing foaming agent；
S4, particle III will be blended made from step S3 and move into and risen in the thermostatic equipment of the particle softening temperature, through one After section soaking time, the block polyetheramides expanded particle with sandbag structure can be obtained.
Further, in parts by weight, modifying agent is 2~15 parts, filler is 1~5 part, coupling agent be 0.003~ 0.1 part, block polyetheramides be 100 parts, environment-friendly physical blowing agent be 10~60 parts.
Further, the modifying agent is thermoplastic polyurethane, HTPS, acrylonitrile-butadiene-phenylethylene One or more in copolymer, low density polyethylene (LDPE), polypropylene, ethylene-vinyl acetate copolymer, EPDM；
The filler is the one or more among calcium carbonate, talcum powder, kaolin, silica or barium sulfate；
The coupling agent is that silane coupler and titanate coupling agent any of are worked as or its mixture；
The hardness of the block polyetheramides is shore D20-60.
The environment-friendly physical blowing agent is carbon dioxide, one kind or more among nitrogen, pressure-air, argon gas Kind.
Further, in the step 3, the autoclave temp is 35-60 DEG C, pressure 4-24Mpa, and time of penetration is 0.5-8 hours, pressure release emptying time are the 20-60 seconds.
Further, in the step S4, thermostatic equipment is blast drier, fluid bed, oil bath pan or can be passed through steam Reactor, the temperature of thermostatic equipment is 100-200 DEG C, and constant temperature time is the 5-60 seconds.
Further, in the step S1 and S2, it is mixed is carried out in dispersion machine in advance, melt blending enters in an extruder OK.
Further, in the blending particle I, filler is core, and modifying agent is shell.
Further, in the step 2, the obtained sandbag structure block polyetheramides blending single weight of particle that has is 4-50mg, draw ratio 5：1.
Further, in the step 4, what is obtained has sandbag structure block polyetheramides expanded particle, and density is 0.01-0.5g/cm3, the sub- weight of individual particle is in 4-50mg, draw ratio 5：1.
Further, in the blending particle III, the content of foaming agent is 0.5%-20%.
By such scheme, the present invention at least has advantages below：
(1) foaming agent used in the present invention is entirely environment-friendly foaming agent, and pollution is not present to environment；
(2) method of the present invention is obtained has sandbag structure block polyetheramides expanded particle, because it has sand Bag structure, possesses the impact strength and toughness higher than other foamed materials, and permanent deformation can also reduce.
(3) block polyetheramides foamed product prepared by the method for the invention, rebound performance are any better than in the market A foamed product, can reach 85%；
(4) filler is with the addition of in block polyetheramides foamed material of the present invention, on the one hand can improves foamed material Mechanical property, on the other hand can reduce material cost；
(5) foamed material prepared by the present invention does not crosslink all, can carry out melting recovery again, reduces environment and gives up The generation of thing.
(6) the block polyetheramides foamed product being prepared with method of the present invention, density is from 0.01-0.5g/ Cm3 can be adjusted arbitrarily, and density is controllable.
Described above is only the general introduction of technical solution of the present invention, in order to better understand the technological means of the present invention, And can be practiced according to the content of specification, below with presently preferred embodiments of the present invention and coordinate accompanying drawing describe in detail as after.
Brief description of the drawings
The block polyetheramides expanded particle scanning electron microscope (SEM) photograph (SEM) of Fig. 1 sandbag structures of the present invention.
Embodiment
With reference to the accompanying drawings and examples, the embodiment of the present invention is described in further detail.Implement below Example is used to illustrate the present invention, but is not limited to the scope of the present invention.
Technical scheme is as follows：
A kind of preparation method with sandbag structure block polyetheramides expanded particle, comprises the following steps：
S1, by modifying agent, filler, coupling agent premix, then by after premix raw materials melt be blended, through granulation underwater or tank The blending particle I with core shell structure is prepared after pelletizing；
S2, the blending particle I that step S1 is prepared and block polyetheramides raw material premix, then by the raw material after premix Melt blending, the block polyetheramides blending particle II with sandbag structure is made after granulation underwater or tank blank；
S3, particle II will quantitatively be blended put into autoclave, autoclave is adjusted to certain temperature and keeps constant temperature, then is passed through Quantitative environment-friendly physical blowing agent, through certain time of penetration until foaming agent and G2 blending particles reach homogeneous system Afterwards, then by relief valve by the pressure in kettle empty, take out the block polyetheramides blending particle III containing foaming agent.
S4, particle III will be blended made from step S3 and move into and risen in the thermostatic equipment of the particle softening temperature, through one After section soaking time, the block polyetheramides expanded particle with sandbag structure can be obtained.
Further, in parts by weight, modifying agent is 2~15 parts, filler is 1~5 part, coupling agent be 0.003~ 0.1 part, block polyetheramides be 100 parts, environment-friendly physical blowing agent be 10~60 parts.
Further, the modifying agent is thermoplastic polyurethane, HTPS, acrylonitrile-butadiene-phenylethylene One or more in copolymer, low density polyethylene (LDPE), polypropylene, ethylene-vinyl acetate copolymer, EPDM；
The filler is the one or more among calcium carbonate, talcum powder, kaolin, silica or barium sulfate；
The coupling agent is that silane coupler and titanate coupling agent any of are worked as or its mixture；
The hardness of the block polyetheramides is shore D20-60.
The environment-friendly physical blowing agent is carbon dioxide, one kind or more among nitrogen, pressure-air, argon gas Kind.
Further, in the step 3, the autoclave temp is 35-60 DEG C, pressure 4-24Mpa, and time of penetration is 0.5-8 hours, pressure release emptying time are the 20-60 seconds.
Further, in the step S4, thermostatic equipment is blast drier, fluid bed, oil bath pan or can be passed through steam Reactor, the temperature of thermostatic equipment is 100-200 DEG C, and constant temperature time is the 5-60 seconds.
Further, in the step S1 and S2, it is mixed is carried out in dispersion machine in advance, melt blending enters in an extruder OK.
Further, in the blending particle I, filler is core, and modifying agent is shell.
Further, in the step 2, the obtained sandbag structure block polyetheramides blending single weight of particle that has is 4-50mg, draw ratio 5：1.
Further, in the step 4, what is obtained has sandbag structure block polyetheramides expanded particle, and density is 0.01-0.5g/cm3, the sub- weight of individual particle is in 4-50mg, draw ratio 5：1.
Further, in the blending particle III, the content of foaming agent is 0.5%-20%.
The embodiment of the present invention is as follows：
Embodiment 1
20kgTPU, 50kg talcum powder and 0.15kg KH550 silane couplers are premixed in dispersion machine, then through double spiral shells Core shell structure blending particle I 60kg is made in bar comminutor melt blending.
The above-mentioned blending 60kg of particle I and 1000kg being prepared block polyetheramides are premixed again, then extruded machine Melt blending, underwater blank, it is 18mg that individual particle weight, which is made, draw ratio 2, has the block polyetheramides spindle of sandbag structure Shape blending particle II 1030kg.
Weigh 500kg blending particles II to put into autoclave, constant autoclave temp is 35 DEG C, is passed through 250kg titanium dioxides Carbon and 50kg argon gas, pressure reach 24MPa, constant temperature 0.5 hour in autoclave, to be infiltrated when reaching balance, are existed with relief valve 20 second stipulated time, whole pressure in kettle are emptied, take out the 500kg of blending particle III that foaming agents content is 10%.
Above-mentioned 500kg blending particles III are moved into and had warmed up to 174 DEG C of vibrated fluidized beds, constant temperature 60 seconds, are obtained close Spend for 0.14g/cm3, draw ratio 2, the block polyetheramides spindle expanded particle with sandbag structure.
Embodiment 2：
150kgEPDM, 10kg calcium carbonate and 0.2kg LK-132 titanate coupling agents are premixed in dispersion machine, then passed through Core shell structure blending particle I 154kg is made in dual-screw pelletizer melt blending.
The above-mentioned blending 154kg of particle I and 1000kg being prepared block polyetheramides are premixed again, then extruded machine Melt blending, underwater blank, it is 4mg that individual particle weight, which is made, draw ratio 1, has the block polyetheramides of sandbag structure spherical The 1150kg of particle II is blended.
Weigh 500kg blending particles II to put into autoclave, constant autoclave temp is 60 DEG C, is passed through 250kg titanium dioxides Carbon and 50kg nitrogen, pressure reach 24MPa, constant temperature 8 hours in autoclave, to be infiltrated when reaching balance, with relief valve 60 Stipulated time second, whole pressure in kettle are emptied, take out the 500kg of blending particle III that foaming agents content is 20%.
Above-mentioned 500kg blending particles III are moved into and had warmed up to 200 DEG C of vibrated fluidized beds, constant temperature 60 seconds, are obtained close Spend for 0.01g/cm3, draw ratio 1, the spherical expanded particle of block polyetheramides with sandbag structure.
Embodiment 3：
100kgLDPE, 20kg silica and 0.2kg KH570 silane couplers are premixed in dispersion machine, then through double Core shell structure blending particle I 118kg is made in screw pelletizer melt blending.
The above-mentioned blending 118kg of particle I and 1000kg being prepared block polyetheramides are premixed again, then extruded machine Melt blending, underwater blank, it is 50mg that individual particle weight, which is made, draw ratio 5, has the block polyetheramides spindle of sandbag structure Shape blending particle II 1110kg.
Weigh 500kg blending particles II to put into autoclave, constant autoclave temp is 50 DEG C, is passed through 50kg titanium dioxides Carbon, pressure reach 4MPa, constant temperature 0.5 hour in autoclave, to be infiltrated when reaching balance, with relief valve when providing within 30 seconds Between, whole pressure in kettle are emptied, take out the 500kg of blending particle III that foaming agents content is 0.5%.
Above-mentioned 500kg blending particles III are moved into and had warmed up to 100 DEG C of air dry ovens, constant temperature 30 seconds, are obtained close Spend for 0.5g/cm3, draw ratio 5, the block polyetheramides spindle expanded particle with sandbag structure.
The present invention at least has advantages below：
(1) foaming agent used in the present invention is entirely environment-friendly foaming agent, and pollution is not present to environment；
(2) method of the present invention is obtained has sandbag structure block polyetheramides expanded particle, because it has sand Bag structure, possesses the impact strength and toughness higher than other foamed materials, and permanent deformation can also reduce.
(3) block polyetheramides foamed product prepared by the method for the invention, rebound performance are any better than in the market A foamed product, can reach 85%；
(4) filler is with the addition of in block polyetheramides foamed material of the present invention, on the one hand can improves foamed material Mechanical property, on the other hand can reduce material cost；
(5) foamed material prepared by the present invention does not crosslink all, can carry out melting recovery again, reduces environment and gives up The generation of thing.
(6) the block polyetheramides foamed product being prepared with method of the present invention, density is from 0.01-0.5g/ Cm3 can be adjusted arbitrarily, and density is controllable.
Described above is only the preferred embodiment of the present invention, is not intended to limit the invention, it is noted that for this skill For the those of ordinary skill in art field, without departing from the technical principles of the invention, can also make it is some improvement and Modification, these improvement and modification also should be regarded as protection scope of the present invention.

Claims (10)

1. a kind of preparation method with sandbag structure block polyetheramides expanded particle, it is characterised in that comprise the following steps：
S1, by modifying agent, filler, coupling agent premix, then by after premix raw materials melt be blended, through granulation underwater or tank pelletizing The blending particle I with core shell structure is prepared afterwards；
S2, the blending particle I that step S1 is prepared and block polyetheramides raw material premix, then by the raw materials melt after premix Blending, the block polyetheramides blending particle II with sandbag structure is made after granulation underwater or tank blank；
S3, particle II will quantitatively be blended put into autoclave, autoclave is adjusted to certain temperature and keeps constant temperature, then is passed through quantitative Environment-friendly physical blowing agent, through certain time of penetration until foaming agent and G2 blending particle reach homogeneous system after, then The pressure in kettle is emptied by relief valve, takes out the block polyetheramides blending particle III containing foaming agent；
S4, particle III will be blended made from step S3 and move into and risen in the thermostatic equipment of the particle softening temperature, through one section of guarantor After the warm time, the block polyetheramides expanded particle with sandbag structure can be obtained.
2. a kind of preparation method with sandbag structure block polyetheramides expanded particle according to claim 1, it is special Sign is：
In parts by weight,
Modifying agent is 2~15 parts, filler is 1~5 part, coupling agent is 0.003~0.1 part, block polyetheramides are 100 parts, ring Border close friend's physical blowing agent is 10~60 parts.
3. a kind of preparation method with sandbag structure block polyetheramides expanded particle according to claim 2, it is special Sign is：
The modifying agent is thermoplastic polyurethane, HTPS, acrylonitrile-butadiene-phenylethylene copolymer, low-density One or more in polyethylene, polypropylene, ethylene-vinyl acetate copolymer, EPDM；
The filler is the one or more among calcium carbonate, talcum powder, kaolin, silica or barium sulfate；
The coupling agent is that silane coupler and titanate coupling agent any of are worked as or its mixture；
The hardness of the block polyetheramides is shore D20-60.
The environment-friendly physical blowing agent is carbon dioxide, the one or more among nitrogen, pressure-air, argon gas.
4. a kind of preparation method with sandbag structure block polyetheramides expanded particle according to right wants 1, its feature It is：In the step 3, the autoclave temp is 35-60 DEG C, pressure 4-24Mpa, and time of penetration is 0.5-8 hours, is let out Pressure emptying time is the 20-60 seconds.
5. a kind of preparation method with sandbag structure block polyetheramides expanded particle according to right wants 1, its feature It is：In the step S4, thermostatic equipment is blast drier, fluid bed, oil bath pan or the reactor that can be passed through steam, constant temperature The temperature of equipment is 100-200 DEG C, and constant temperature time is the 5-60 seconds.
6. a kind of preparation method with sandbag structure block polyetheramides expanded particle according to right wants 1, its feature It is：In the step S1 and S2, it is mixed is carried out in dispersion machine in advance, melt blending is carried out in an extruder.
7. a kind of preparation method with sandbag structure block polyetheramides expanded particle according to right wants 1, its feature It is：In the blending particle I, filler is core, and modifying agent is shell.
8. a kind of preparation method with sandbag structure block polyetheramides expanded particle according to right wants 1, its feature It is：In the step 2, the obtained sandbag structure block polyetheramides blending single weight of particle that has is 4-50mg, major diameter Than for 5：1.
9. a kind of preparation method with sandbag structure block polyetheramides expanded particle according to right wants 1, its feature It is：In the step 4, what is obtained has a sandbag structure block polyetheramides expanded particle, density 0.01-0.5g/cm3, The sub- weight of individual particle is in 4-50mg, draw ratio 5：1.
10. a kind of preparation method with sandbag structure block polyetheramides expanded particle according to right wants 1, its feature It is：In the blending particle III, the content of foaming agent is 0.5%-20%.
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CN201711053875.8A CN107629448B (en) 2017-10-31 2017-10-31 Preparation method of block polyether amide foaming particles with sand bag structure
JP2019527498A JP6852921B2 (en) 2017-10-31 2017-12-12 Method for Producing Block Polyetheramide Effervescent Granules Containing Sandbag Structure
PCT/CN2017/115520 WO2019085158A1 (en) 2017-10-31 2017-12-12 Method for preparing block polyether amide foamed particle with sandbag structure
US16/469,974 US11124619B2 (en) 2017-10-31 2017-12-12 Method for preparing block polyether amide foam particles with sandbag structure
EP17917218.4A EP3517574A4 (en) 2017-10-31 2017-12-12 Method for preparing block polyether amide foamed particle with sandbag structure
KR1020197023864A KR102263684B1 (en) 2017-10-31 2017-12-12 Method for producing block polyether amide expanded particles having a sandbag structure

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